JPS62109976A - Member covered with cubic boron nitride - Google Patents

Abstract

PURPOSE:To prepare a member covered with cubic boron nitride having improved resistance to delamination of the coating layer prepd. by interposing a layer contg. Si as an intermediate layer in the stage for forming an external layer consisting essentially of cubic boron nitride on the surface of a base body. CONSTITUTION:In the stage of prepg. a covered member by forming an external layer consisting essentially of cubic boron nitride on the surface of a base body, intermediate layer(s) constituted of a single or multiple layers is(are) interposed between the base body and the external layer, and the intermediate layer adjacent to the external layer is formed of a layer contg. at least one Si compd. selected from Si, Si-Al alloy, Si-Al nitride, and silicon nitride. If the external layer is constituted of cubic boron nitride, the thickness of the layer is regulated to ca. 0.1-15mu. If a binding phase is contained in addition to cubic boron nitride in the external layer, the thickness of the layer is regulated to ca. 0.05-0.8mm. By this constitution, a covered member having a dense film external layer is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a seriously ill boron nitride-coated member that can be used as tool parts such as cutting tools or wear-resistant tools, and parts for electronic devices such as semiconductor substrates. .

(Prior art) Cubic boron nitride has high hardness, high thermal conductivity, and high gas insulation properties that are second only to diamond, and also has better chemical stability, oxidation resistance, and heat resistance than diamond. and # has thermal shock properties.

In addition, diamond has a high affinity with iron group metals, whereas cubic boron nitride has a low affinity with iron group metals, so it can be used as a tool material for cutting or grinding iron group metal materials, for example. It is attracting attention as As described above, although cubic boron nitride has excellent properties, it is a brittle material and is difficult to sinter, so its shape and use are limited.

Therefore, attempts have been made to solve the shape and usage constraints by using a covering member formed by forming a covering layer of cubic boron nitride on the surface of the substrate. As a typical example, a coating member made by forming a cubic boron nitride coating layer directly on the surface of a silicon nitride sintered body is disclosed in Japanese Patent Laid-Open No. 57-9.
It is disclosed in Japanese Patent No. 5881.

(Problems to be Solved by the Invention) The covering member disclosed in JP-A-57-95881 has the following problems. The silicon nitride sintered body contains a sintering aid mainly composed of metal oxides such as A1203, MgO, Y203 fZ, etc. to promote sintering. In this way, a coated member in which a coating layer made of cubic boron nitride is directly formed on the surface of a silicon nitride sintered body substrate containing a sintering aid, has the sintering aid present on the surface of the substrate as well. , the sintering aid inhibits the conversion of boron nitride, such as hexagonal boron nitride or amorphous boron nitride, to cubic boron nitride,
Furthermore, there is a problem in that the adhesion between the substrate and the coating layer is reduced.

The present invention solves the above-mentioned problems. Specifically, the present invention has the effect of promoting the conversion of boron nitride to cubic boron nitride between the substrate and the outer layer made of cubic boron nitride. The object of the present invention is to provide a cubic boron nitride coated member which has an intermediate layer interposed therein which has excellent stability at high temperatures and excellent adhesion to the outer layer.

(Means for solving the problem) When a coating layer made of cubic boron nitride is formed on the surface of a substrate, there are two forms. In the first form, cubic boron nitride is synthesized, This is the case when the cubic boron nitride is deposited on the surface of the substrate as a coating layer, and the second
The form of boron nitride, such as amorphous boron nitride or hexagonal boron nitride, is converted to cubic boron nitride at the same time or after it is deposited as a coating layer on the surface of the substrate. This is the case. Among these, for the first form, a substance to which cubic boron nitride easily adheres is required, and for the second form f8, a substance that is excellent in converting boron nitride to cubic boron nitride is required. The present inventor has studied the materials necessary for the first form and the second form and materials that can withstand harsh uses such as tool parts, and found that oxygen Further, since oxygen-containing compounds are the most impediment to the first form and the second form, and carbon and carbon-containing compounds are also unfavorable to the first form and the second form, As a result of investigation, silicon, silicon aluminum alloy, silicon nitride, or silicon aluminum nitride is J:
The present invention has been completed by finding that the first and second embodiments described above can be satisfied.

That is, in the cubic boron nitride-coated member of the present invention, in the W1 member formed by forming an outer layer mainly composed of cubic boron nitride on the surface of a base, one layer or multiple layers are provided between the base and the outer layer. interposed therebetween, and the intermediate layer adjacent to the outer layer is formed of a silicon-containing material layer consisting of at least one of silicon, silicon-aluminum alloy, silicon-aluminum nitride, or silicon nitride. It is characterized by this.

The substrate used here is not particularly limited as long as it is made of a material that can withstand the manufacturing conditions described below, such as various types of full-flexure 9 alloys and sintered high speed steel.

Cemented carbide, cermet, ceramics, etc. can be used depending on the purpose.

The outer layer containing cubic boron nitride as one component can be formed as a thin layer on the order of μm to a thick layer on the order of am. The components of this outer layer include Fe in addition to cubic boron nitride or cubic boron.

Ni, Co, A-text, Si and periodic table 4a.

Contains at least one binder phase selected from group 5a, 6a metals or nitrides of An, Si, or carbides, nitrides, borides of group 4a, 5a, and 6a metals of the periodic table, and mutual solid solutions thereof. can be made into something. Among these, in the case of the outer layer made of cubic boron nitride, since cubic boron nitride is a brittle material,
Layer thickness of 15 μm or more, preferably 0.5 μm or more. -t
It is preferable to form a thin film with a layer thickness of 0.0 m or less, and in the case of an outer layer containing a binder phase in addition to boron nitride M, a layer thickness of 0.0 m or less is preferable.
It is also possible to form an Iγ film with a layer thickness of 0.5 m or less and 0.8 m or less.

The intermediate layer interposed between these substrates and the outer layer may be of various types depending on the material of the substrate used or the use or shape of the covering member of the present invention. can be made into

For example, in a first configuration, the intermediate layer comprises a layer of at least one silicon-containing material selected from silicon, a silicon-aluminum alloy, a silicon-free aluminum nitride, or a silicon-containing nitride. In this case, a silicon-containing layer is interposed between the base and the outer layer, and the material has excellent adhesion to the silicon-containing layer, such as AfLN ceramics.

A! Q20] type ceramics, SiC type ceramics, or Si3N+ type ceramics including Sialon.

When applied to a substrate such as wood, the excellent properties of the outer layer can be exhibited.

In a second configuration, the intermediate layer consists of a silicon-containing layer and a 1″fF:4 auxiliary layer of at least one of aluminum oxide, aluminum nitride, and aluminum oxynitride. In this case, A first fi between the base and the outer layer
An adhesion auxiliary layer and a silicon-containing layer are interposed, the first g adhesion auxiliary layer is adjacent to the substrate, and the silicon-containing layer is adjacent to the outer layer, and has excellent adhesion with the first adhesion auxiliary layer. base body
For example, when applied to a substrate made of Zr0p ceramics, TiC ceramics, or various ceramics, the outer layer exhibits excellent properties.

As a third structure, the intermediate layer is a silicon-containing material layer, a first adhesion auxiliary layer, and a carbide of a group 4a, 5a, or 6a metal of the periodic table;
a 2nd v:4 auxiliary layer of at least one of nitrides, oxides and phase q solid solutions thereof. In this case, a 52 adhesion auxiliary layer, a first nursing care auxiliary layer, and a silicon-containing layer are interposed between the base and the outer layer, the second adhesion auxiliary layer is adjacent to the base, and the silicon-containing layer is provided as the outer layer. The first adhesion auxiliary layer is adjacent to the second adhesion auxiliary layer and the silica-containing material layer, and the material has excellent adhesion to the second adhesion auxiliary layer, e.g. When applied to various metals or substrates such as stealth steel, high-speed steel, various alloys including steel, sintered high speed steel, 8 hard alloy, cermet, etc., the excellent properties of the outer layer can be exhibited.

Other intermediate layer configurations include, for example, +i? In the third structure mentioned above, a layer made of metal or alloy is further interposed between the base and the second adhesion auxiliary layer, or a combination of a silicon-containing layer and a second adhesion auxiliary layer as the intermediate layer. It can also be done.

As mentioned above, the intermediate layer can be made from one layer or multiple layers, but the intermediate layer adjacent to the outer layer has excellent adhesion with cubic boron nitride and boron nitride. It is characterized by the use of a silicon-containing layer because of its high FJ and excellent strength and chemical stability.

Specifically, these intermediate layers include, for example, Si and 5i-A12 alloy as the silicon-containing layer.

(Si, Party A) N, Si:Na, and the 1st occupation support layer is 1, for example, A standing, 0], A...QN.

There is a sentence A (N, O), and the second adhesion auxiliary layer is:
For example, T i C, Z r C, Hf C, V C.

TaC1NbC, Cr3C7, Cr7C3.

MQ7 C, WC, TiN, ZrN, VN.

TaN, CrN, Tie, TiC2, ZrC1.

Ta, +05, Ti (N, C).

(Ti-Ta)C, (Ti-Fist W)C.

Ti (N, O), Ti (C, N, O).

(Ti.Ta-W)C, etc. can be mentioned. These intermediate layers may be formed not only as chemical compounds but also as non-chemical compounds, and among non-chemical compounds, metal light, non-gold J1 for E, etc.
In some cases, it is formed as a subchemical clay heavy compound, which is smaller than the former.

The cubic boron nitride coated member of the present invention can be manufactured by the following method. First, the substrate can be used in the form of a plate, a block, a powder, or a compacted powder. When used as a plate or block, it is preferable to polish, wash, dry, etc. the surface of the substrate as necessary to improve adhesion between the substrate and the intermediate layer.

, +1 (The method of providing an intermediate layer on the surface of the body is the CVD method,
Method using PVD method or plasma CVD method.

There are two methods: a method of carburizing or nitriding the metal after 74 hours to form an intermediate layer of a metal compound, a method of providing it as a powder by spraying or brush coating, or a method of providing it as a compacted powder by pressure molding. ), (If it is necessary to provide a layer made of metal or alloy on the surface of the substrate in order to improve the adhesion between the body and the intermediate layer, vaporization, ion-blating, or coating such as In addition to the PVD method, it can also be formed by plating.

In addition to the PVD method or plasma CVD method, the outer layer can be formed in the form of powder, powder compact, CVD method, PVD method,
After boron nitride is formed on the surface of the intermediate layer by a plasma CVD method or the like, it can be treated under stable high pressure and high temperature conditions for cubic boron nitride to form an outer layer mainly composed of cubic boron nitride. Furthermore, to specifically explain the method for manufacturing the coated member of the present invention, in the first method, the base body is a plate-shaped body or a block body made of, for example, a wire drawing, a rolled product, a cast product, a forged product, or a sintered crystal. In this case, after polishing, cleaning and drying the surface of the substrate, an intermediate layer is provided by CVD, PVD or plasma CVD. Next, a method of forming a thin film-like outer layer of about 0.05 m to 20 SLm on the surface of the intermediate layer by placing it in a reaction vessel such as PVD method, plasma CVD method, or laser evaporation method that can generate high energy. It is.

In the second method, an intermediate layer is formed on the surface of the same substrate as used in the first method in the same manner as in the first method, and then the surface of the intermediate layer is coated with CVD, PVD, plasma CVD, or laser. To form the outer layer by the thin stone method, for example, a thin film made of amorphous boron nitride or 60,000 boron nitride is formed, and then a belt-type or kirtle-type high-pressure, high-pressure film is used. !
This is a method in which boron nitride is installed in a device and treated under stable high-pressure and high-temperature conditions.

In the third glue method, after forming an intermediate layer in the same manner as in the first method on the surface of the same substrate as used in the first method, a thick film of about 0.05+s+s to 0.8 mist is formed. For the purpose of forming the outer layer of the epigonal boron nitride, a powder or compacted powder material for forming the outer layer is provided on the surface of the intermediate layer, and then placed in a high-pressure and high-temperature device to form a stable high-pressure and high-temperature product of the epigonal boron nitride. This method uses conditional processing. At this time, when forming a thick outer layer, it is preferable to contain, in addition to boron nitride M, a substance such as aluminum nitride, which acts as a catalyst for the conversion of boron nitride to serious boron nitride. It is.

The fourth method is to provide an intermediate layer made of powder, compacted powder, or plate on the surface of the same substrate as used in the first method, and then form an outer layer on the surface of this intermediate layer. A powder or compacted powder is prepared for the purpose, and then placed in a high-pressure and high-temperature device to ensure that the seriously ill boron nitride is stable under 5-pressure and high-temperature conditions.
This is a method of processing.

The fifth method is to provide the base, intermediate layer, and outer layer in the form of powder or compacted powder, and then place them in a high-pressure and high-temperature device to process cubic boron nitride under stable high-pressure and high-temperature conditions. It is.

The stable high-pressure and high-temperature conditions r for cubic boron nitride at this time can be carried out at a pressure of 4.5 GPa or higher and a temperature of 700°C, but in particular a pressure of 6.0 GPa or higher and a temperature of 1500°C.
It is preferable to carry out the reaction at a temperature below .degree.

(Function) In the cubic boron nitride-coated member of the present invention, since the intermediate layer adjacent to the outer layer is a silicon-containing layer, the adhesion between the outer layer made of cubic boron nitride and the intermediate layer is improved, and the nitrided The purpose of this treatment is to enhance the conversion effect of boron into serious boron nitride. For this reason, the coated member of the present invention has a high cubic boron nitride content even if the outer layer is formed using a high-energy PVD method or plasma CVD method, and a dense, film-like outer layer is likely to be formed. Even if the outer layer is formed under stable high-pressure and high-temperature conditions using cubic boron nitride, the content of cubic boron nitride is high and the outer layer is dense in wI. As a result, the coated member of the present invention can fully exhibit the various properties of cubic boron nitride itself, such as high hardness, high thermal conductivity, and high electrical insulation.

(Example) Example I S iz Na -8wt%A120z -4wt%Y
Shape and dimensions 1 made of ceramic sintered body with 2O3 composition
After polishing the surface of the 0 φ x 3 mm substrate with a diamond grindstone, the substrate was washed with distilled water and ethyl alcohol, and dried.Then, the substrate was placed in a container of a CVD device, and 10vo%5iCua = 40va1%NH3-50vou%H
240vo 1 pressure cuff 0Torr, temperature 1f! LL
Processed at 100°C for 50 minutes (a silicon nitride layer was formed on the surface of the body) Next, after evacuating the residue in the container, 1 Ovou% BC1 = -25vo1
%H7-35voi%NH3-30vo1%In Ar atmosphere, pressure 50Torr, temperature 1200℃, holding time 12
The surface iI′i′i of the silicon nitride layer was treated under conditions of 0 minutes.
A layer of boron nitride was then formed. The boron nitride layer at this time was examined by X-ray diffraction and was found to be composed of amorphous boron nitride. This was placed in a high-pressure, high-temperature device and treated under conditions of a pressure cuff, 0 GPa, and a temperature of 1600° C. to obtain a coated member of the present invention.

For comparison, a comparative coated member was obtained by performing the same steps as described above except for the step of forming the silicon nitride layer.

When the coating layers of the thus obtained coated member of the present invention and the comparative member 1'a were examined using X-ray diffraction and a scanning doublet microscope, it was found that the coated member of the present invention had a dense outer layer with a thickness of 3 μm. A layer of cubic boron nitride, with an intermediate layer of 5i3N with a thickness of 2 pm.
A layer, and the comparative coated member had a coating layer with a thickness of 3 gm, and was a layer of hexagonal boron nitride, V containing crystalline boron nitride. The properties were determined using a scratch tester equivalent to a scratch hardness tester.
In the coated member of the present invention, the coating layer did not peel off even when scratched with a diamond pressure T with a load of 100 kg.
When the comparative coated member was scratched with a diamond indenter to which a 6 kg ball was applied, the coating layer peeled off.

Example 2 After treating the surface of a 10 φ x 3 mm substrate made of a ceramic sintered body with Zr07-3wt%MgO composition in the same manner as in Example 1, it was placed in a reaction chamber and 5vof
1%AC13-10vau%C0-10vau%CO7
-75vafL%H2 atmosphere, pressure 30Torr
A layer of aluminum oxide was formed on the surface of the substrate by treatment at a temperature of 1100° C. and a holding time of 120 minutes. Next, after evacuating the gas in the container, 10vo exchange% SiC
text, -50vai%NN7-40vo%H2 atmosphere,
A silicon nitride layer was formed on the surface of the aluminum oxide layer by treatment at a pressure of 50 Torr, a temperature of 1200°C, and a holding time of 30 minutes, and after evacuating the scum in the ilfl volume, 10 vou% BC1+ -'25 vou% H ,・35
vo, i%NH3-30voQ%Ar atmosphere, pressure 5
A layer of boron nitride was formed on the surface of the silicon nitride layer by processing at a temperature of 0 Torr, a temperature of 1200°C, and a holding time of 120 minutes.Next, it was placed in a high pressure and high temperature treatment, and a pressure of 6.0
GPa and a temperature of 1600° C. to obtain a coated member of the present invention.

For comparison, from the method for producing a coated member of the present invention described above, except for the step 1 of forming an aluminum oxide layer and the step 1 of forming a nitride layer on silicon, After forming the layer, it was similarly subjected to high pressure and high temperature treatment to obtain a comparative coated member.

The coated member of the present invention thus obtained and the comparative coated member were examined in the same manner as in Example 1, and it was found that the outer layer of the coated member of the present invention was a dense cubic boron nitride layer with a thickness of 3 pm, and the middle layer was a dense cubic boron nitride layer with a thickness of 3 pm. The layers are Au203 layer with a thickness of Igm and Si:Nn with a thickness of 1 tile.
The comparative coated member had a thickness of 3 μm and was a layer of hexagonal boron nitride.

Example 3 After treating the surface of a 10×10×5+sm substrate made of cemented carbide with a WC-5wt% CO composition in the same manner as in Example 1, it was placed in a reaction vessel and 8voM%Ti
Ci4-5voJ1%CHa -87va1%H2 atmosphere, pressure 20 Torr, temperature 1000°C, holding time 3
After processing for 0 min to form a titanium carbide layer, the gas in the container was evacuated, and then 5 min 0 m% AlC1
x -10voJIL%C0-10vou%CO2-7
In a 5vofL%H2 atmosphere, the pressure was 30Torr,
After processing at a temperature of 1100°C and a holding time of 120 minutes to form an aluminum oxide layer on the surface of the titanium carbide layer, and evacuating the gas in the container again, 10vai% Si
A silicon nitride layer was formed on the surface of the aluminum oxide layer by processing in an Ala-50vol%N2-40vou%H2 atmosphere at a pressure of 50 Torr, a temperature of 1200°C, and a holding time of 30 minutes. In addition, after evacuating the gas in the container, plasma is generated in the container by a high-output variable high-frequency thermal plasma generator, and 20 voJ1%B3 N3 H6-40voi%NH
:l-40mm% H2 atmosphere at a temperature of 1600 DEG C. to form a layer of boron nitride on the surface of the silicon nitride layer to obtain a coated member of the present invention.

For comparison, a comparative coated member was obtained by directly forming a boron nitride layer on the surface of the substrate using the method for forming a boron nitride layer described above.

The coated member of the present invention thus obtained and the comparative coated member were examined in the same manner as in Example 1, and it was found that the coated member of the present invention had an outer layer mainly composed of cubic nitride with a thickness of 2 gm. A pattern 20 where the intermediate layer is a TiC layer with a thickness of Igm and a thickness of lJLm
The comparative covering member was composed of three layers and a 5ixNn layer with a thickness of 1 m, and the coating layer was only adhered in some places.

Example 4 After coating the surface of a substrate made of a Mo plate with a Si film using ion plate ink, it was placed in a CVD apparatus for 1 hour.
0 ma 0 sentence % BC standing 3-25 ma 0 standing % H2-35 van%
In NH3-30va 1% Ar atmosphere.

Pressure 50Torr, temperature 1300℃, holding time 1
A boron nitride layer was formed on the surface of the Si layer under conditions of 20 minutes. Next, it is installed in a high-pressure and high-temperature device, and the pressure is 6 GPa.
A coated member of the present invention was obtained by processing at a temperature of 1200°C.

For comparison, a comparative coated member was obtained by directly forming a boron nitride layer on the surface of a Mo plate substrate using the method for forming a boron nitride layer described above.

The thus obtained coating layers of the coated member of the present invention and the comparative coated member were examined in the same manner as in Example 1.1 The coated member of the present invention had an outer layer of cubic boron nitride with a thickness of 3 μm, and an intermediate layer of cubic boron nitride. The layer is composed of a Si layer with a thickness of 2 m, and the comparative covering member is
The covering layer was a hexagonal boron nitride layer.

(Effects of the Invention) As described above, the cubic boron nitride-coated member of the present invention has an intermediate layer interposed between the substrate and the outer layer containing cubic boron nitride as a main component, thereby increasing the durability of the coating layer. It has extremely excellent releasability and has a dense outer layer made of t-gonal boron nitride. For this reason, it can be applied not only to cutting tools and wear-resistant tools in which conventional sintered boron nitride bodies are used, but also to tool members that are subject to restrictions in terms of shape and use. In addition, since the outer layer made of cubic boron nitride is dense and has little variation, the characteristics of cubic boron nitride can be used for industrial H4T applications, which can be applied to various electrical and electronic components, including conductor substrates. It is the material.

Claims (3)

[Claims] (1) In a covering member formed by forming an outer layer mainly composed of cubic boron nitride on the surface of a substrate, an intermediate layer composed of one layer or multiple layers is interposed between the substrate and the outer layer, and the A cubic boron nitride-coated member, characterized in that the intermediate layer adjacent to the outer layer is formed by a silicon-containing layer consisting of at least one of silicon, silicon-aluminum alloy, silicon-aluminum nitride, or silicon nitride. . (2) The intermediate layer is composed of a silicon-containing layer adjacent to the outer layer and an adhesion auxiliary layer composed of one layer or multiple layers, and the adhesion auxiliary layer adjacent to the silicon-containing layer is aluminum oxide or aluminum nitride. 2. The cubic boron nitride coated member according to claim 1, wherein the first adhesion auxiliary layer is made of at least one of aluminum oxynitride. (3) In the intermediate layer, the second adhesion auxiliary layer adjacent to the first adhesion auxiliary layer is one selected from carbides, nitrides, oxides, and mutual solid solutions of metals of groups 4a, 5a, and 6a of the periodic table. The cubic boron nitride-coated member according to claim 2, characterized in that the cubic boron nitride-coated member is composed of more than one type of component.